DE1567788A1 - Process for the production of chlorine, bromine or iodine - Google Patents

Description

int. CL:

C Ol b, 7/00

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

German class: 12 i, 7/00

Disclosure 1 567 788

File number: P 15 67 788.0 (S 96672) Filing date: April 21, 1965

Disclosure date: May 27 , 1970

Exhibition priority: -

Union priority Date: Country:
File number:

April 23, 1964

Netherlands

6404460

Designation: 'Process for the production of chlorine, bromine or iodine

Addition to: Removed from: Applicant: Shell Internationale Research Maatschappij, N.V., The Hague

Representative: Wuesthoff, Dr.-Ing. F .; Pulse, Dipl.-Ing. G.; v. Pechmann, Dr. E .; Patent Attorneys, 8000 Munich

Named as inventor: Heemskerk, Jan; Stuiver, Johannes Christian Marinus;

Amsterdam, Netherlands)

Notification according to Art. 7, Paragraph 1, Paragraph 2, No. 1 d. Ges. V. September 4, 1967 (Federal Law Gazette I p. 960): July 5, 1969

O 5.70 009 822 1524

DR. ING. F. WUESTHOFF

DRAt-PECHMAOT PATENT LAWYERS

156778ο

8 MUNICH 9 SOEWErOEHSTHASSE 2

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Dr.

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Munich

1A-29 771

B_j8_ 5 chre ib u_ nj * on the patent application

SHELL INTERMIIONAL RESEARCH MAAiDSOHAPPIJ N.T.

30, Carel van Bylandtlaan, The Hague, Netherlands

: concerning
Ve RfaH ren to Prod e Settin g of chlorine, bromine or Jo d "

The invention relates to the manufacture of Chlorine, bromine or iodine from the compounds of these halogens with hydrogen. The invention is special Importance for the production of chlorine from hydrogen chloride.

A well-known process for the production of halogens from hydrogen halide compounds consists in that the hydrogen halide compounds mixed with oxygen or an oxygen-containing gas come into contact be brought with a catalyst. "With the Deacon process copper compounds are used as, catalyst

.0000-22 / 15-24

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used. There are also compounds of other metals been used as catalysts for this oxidation. In general, "these" are known processes the percentage conversion substantially below that which would correspond to the equilibrium " Only recently have improvements been made in this regard by combining combinations of compounds of copper, rare earths and alkali metals are used »

It has now been found that ruthenium compounds are very effective catalysts for the oxidation of hydrogen chloride, Hydrogen bromide or hydrogen iodide in of the gas phase are »With these catalysts, surprisingly, the equilibrium is already relatively reached lower temperatures.

The invention relates to the production of chlorine, bromine and / or iodine from the corresponding Wasserst off halides by contacting a gaseous mixture of hydrogen halides and oxygen is brought with a catalyst and is characterized in that one or more ruthenium compounds be used as a catalyst.

A very useful ruthenium compound is ruthenium (III) chloride. For the oxidation of hydrogen chloride, temperatures between 250 and 500 ° Ό are used «,

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Temperatures between 325 and 400 ° C are special suitable, but the process can also be carried out well above 4-00 ° C.

In the process according to the invention, atmospheric Prints proved to be very satisfactory. An increase in pressure causes a shift in the equilibrium towards halogen and water, and can therefore be cheap. Although generally the process pressure will not fall outside the range of 1 to 5 ata is, the reaction can in principle both at higher and lower pressures, ζ. BV between 0.1 and 100 ata.

The ruthenium compounds are preferably applied to a carrier. The most common carriers are used with success. Examples of suitable supports include: silica gel, alumina, pumice stone and ceramic material. The amount of ruthenium in the catalyst is usually 0.1-15 wt .- ^ as metal, calculated based on the sum of metal and carrier.

The present catalyst can soiohl in solid layers as well as in fluidized beds.

The oxidation is carried out with gaseous oxygen. Usually the gaseous hydrogen halide will be mixed with air. Except air, however, can

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other oxygen-containing gases as well as pure oxygen can also be used.

In general, the hydrogen halide and oxygen should be in a stoichiometric ratio are to each other. But you can also start from the stoichiometric ratio and use mixtures delete the catalyst, in which the ratio of hydrogen halide to oxygen is between 5 times and 1/5 of the stoichiometric ratio.

The catalyst is applied to the support in a customary manner. Am very suitable procedure in mixing the carrier with as much solution of a ruthenium compound in water as just now can be absorbed by the carrier material. This way the catalyst will be evenly on the Carrier distributed and there is no need to separate any remaining solution. The concentration of Solution is chosen so that the desired ratio of ruthenium to carrier is obtained.

The gaseous mixture used as the starting material can also contain one or more hydrocarbons. In this case, the hydrocarbons react with the halogen formed. This is how halogen can

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to unsaturated alip.hatisch.e-- hydrocarbons are attached, or hydrogen atom® of saturated aliphatic, cycloaliphatic or aromatic hydrocarbons are replaced by halogen «In As a rule, in these cases high conversions of hydrogen halides are achieved with markedly lower ones Temperatures as achieved in the absence of hydrocarbons. Suitable temperatures are often between 100 and 300 ° C.

Example;

Preparation of the catalyst.

As the carrier, there was used silica having the following properties used?

surface 292 .67 m ² / g Pore volume O ml / g Average , 4 Pore diameter 91 .13 1 la salary - O .11 * Fe content O *

The support was dried at 500 ° 0 for 2 hours and several times with a solution of ruthenium (III) chloride soaked. The impregnated © carrier was dried at 100 ° C and finally for 3 hours in a stream of air " heated to 250 ° C.

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The concentration of the solution of ruthenium (HI) chloride was varied in various experiments to produce catalysts with different ruthenium content to obtain. The ruthenium content was expressed as% by weight of the metal, "based on the sum of metal and carrier.

Hers tellung__von chlorine

Hydrogen chloride gas and air were in stoichiometric ratio at atmospheric pressure and at one rate of 60 l / h HCL per kg of catalyst passed over the catalyst. The percentage of Ruthenium in the catalyst and the temperature were varied.

The following table gives the percent conversion values and the equilibrium values for comparison.

Table Ru

5, OO 8th, IV) 12, 91 balance

Temperature, ° C 325 350 30Y) 40 56 - 66 76 44 67 79 46

85 82 79.5

Claims 009822/1524

Claims (3)

Ψ 1 56778 "δ ~""" Pa t en t a η s P_r__ü c_h _e 1, process for the production of chlorine, bromine and / or Iodine, preferably of chlorine, from the corresponding hydrogen halides by creating a gaseous mixture of hydrogen halides and oxygen "brought into contact with a catalyst at elevated temperature is, thereby g e k e η η ze i c h η e t that a or more ruthenium compounds can be used as a catalyst. 2. The method according to claim 1, characterized in that g e k e η η ζ e i c h η. e t that ruthenium (III) chloride is used as the catalyst. 3. "The method according to claim 1 or 2, characterized in that g e k e η η indicates that the temperature is between 325 and 400 ° C. VII II 009822/1524